Chemistry of the Podocarpaceae. XXXIV. Some oxidation products of (13R)-Labda-8(17),14-dien-13-ol (Manool)

1971 ◽  
Vol 24 (11) ◽  
pp. 2365 ◽  
Author(s):  
RC Cambie ◽  
KN Joblin ◽  
AF Preston
Keyword(s):  
Nucleophilic Substitution ◽  
Potassium Permanganate ◽  
Hydroxy Acid ◽  
Methyl Ketone ◽  
Major Product ◽  
Oxidation Products ◽  
Lithium Aluminium Hydride ◽  
Methyl Ketones ◽  
Sodium Dichromate ◽  
Lithium Aluminium

Some products from the oxidation of manool (3) are examined. Potassium permanganate gives, inter alia, the hitherto unreported compound (16) while sodium dichromate gives the methyl ketone (5) and, as the major product, a mixture of (Z)- and (E)-α,β-unsaturated aldehydes (21). Hypoiodite oxidation of the methyl ketone (5) gives the α-hydroxy acid (26) in addition to the expected acid (6). Products of nucleophilic substitution have also been obtained from the hypoiodite oxidation of the methyl ketones (9) and (37). Peracid oxidation of the methyl ketone (5) gives the epoxy acetate (41) which, on reduction with lithium aluminium hydride, affords the diol (7), from which the odoriferous oxide (30) can be prepared. Oxidations leading to formation of the dione (10) are investigated.

Chemistry of the Podocarpaceae. XXII. Aspects of the chemistry of Totara-8,11,13-trien-13-ol

1969 ◽  
Vol 22 (9) ◽  
pp. 1975 ◽  
Author(s):  
RC Cambie ◽  
DR Crump ◽  
RN Duve
Keyword(s):  
Sulphuric Acid ◽  
Methyl Ether ◽  
Major Product ◽  
High Yield ◽  
Lithium Aluminium Hydride ◽  
Birch Reduction ◽  
Transannular Cyclization ◽  
Lithium Aluminium ◽  
Fragmentation Reactions

Attempts have been made to effect fragmentation reactions with bromo- tetralone systems related to 6α-bromo-13-hydroxytotara-8,11,13-trien-7- one (VII), a compound which affords a secoditerpenoid (IX) when treated with DMSO-NaHCO3. On treatment with sulphuric acid in acetone, the mono- epoxide derivative (XXVIII) of the methyl ether of the secoditerpenoid undergoes a novel aromatization to a naphthalenic aldehyde (XXXI) by successive transannular cyclization and fragmentation reactions. ��� A 7β-hydroxy configuration has been confirmed for the major product from reduction of 13-acetoxytotara-8,11,13-trien-7-one (VIII) with lithium aluminium hydride. 13-Methoxytotara-8,11,13-triene (II) has been deisopropylated and then subjected to Birch reduction in an attempt to effect a high yield conversion into (+)-podocarp-8(14)-en- 13-one (XXXVII), a potentially useful intermediate for synthesis.

scholarly journals Study of lithium aluminium hydride reduction of 5-acetyl-1,6-dimethyl-4-phenyl-3,4-dihydropyrimidin-2(1h)-one

2017 ◽  
Vol 15 (1) ◽  
pp. 17-22
Author(s):  
Dragan Zlatkovic ◽  
Niko Radulovic
Keyword(s):  
Chromatographic Separation ◽  
Major Product ◽  
Lithium Aluminium Hydride ◽  
Reaction Products ◽  
Hydride Reduction ◽  
Lithium Aluminium

In this paper, we investigated the LiAlH4-reduction of 5-acetyl-1,6-dimethyl- 4-phenyl-3,4-dihydropyrimidin-2(1H)-one (N-methylated Biginelli compound). Following the reduction and SiO2-promoted dehydration, (Z)-5-ethylidene-1-methyl-6- methylene-4-phenyltetrahydropyrimidin-2(1H)-one was isolated as the major product (33% yield). Chromatographic separation of the reaction products also allowed us to isolate (yield in parentheses) and fully spectrally characterize: 1,6-dimethyl-4-phenyl- 5-vinyl-3,4-dihydropyrimidin-2(1H)-one (20%), 5-ethyl-1,6-dimethyl-4-phenyl-3,4- dihydro-pyrimidin-2(1H)-one (9%), 5-(1-hydroxyethyl)-1,6-dimethyl-4-phenyl-3,4- dihydropyrimidin-2(1H)-one (5%). A possible mechanism explaining the formation of these products is proposed.

Synthesis of Carba Analogues of Deoxy-4-C-(hydroxymethyl)pentofuranoses, Intermediates in the Synthesis of Carbocyclic Nucleosides

1998 ◽  
Vol 63 (12) ◽  
pp. 2044-2064 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Milena Masojídková ◽  
Antonín Holý
Keyword(s):  
Allyl Alcohol ◽  
Major Product ◽  
Protecting Groups ◽  
Carbocyclic Nucleosides ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Benzoyl Group ◽  
Glucose Reduction ◽  
Hydroxy Groups

Racemic dimethyl 4-methoxy- (11 and 12), diallyl 4-allyloxy- (13 and 14) and dimethyl 4-(ethylsulfanyl)-2-hydroxycyclopentane-1,1-dicarboxylates (15 and 16) were prepared by base-catalyzed addition of methanol, allyl alcohol and ethylsulfane, respectively, to dimethyl (4-oxobut-2-en-1-yl)malonate (6). Deallylation of 13 and 14 afforded 4-hydroxycyclopentanes 27 and 28. Reduction of 11-16 with lithium aluminium hydride gave the corresponding 4-substituted 2,2-bis(hydroxymethyl)cyclopentanols. Dimethyl (2S,3S,4R)-, (2R,3S,4R)-3-benzyloxy-4-formyloxy-2-hydroxycyclopentane-1,1-dicarboxylates (35, 36) and dimethyl (2S,3S,4R)-, (2R,3S,4R)-3-benzyloxy-2-benzoyloxy-4-methoxycyclopentane-1,1-dicarboxylates (39, 40) were synthesized starting from D-glucose. Reduction of dimethyl cyclopentane-1,1-dicarboxylates 39 and 40 with lithium aluminium hydride, benzoylation of the formed hydroxy derivatives, hydrogenolysis of benzyl groups, conversion of the liberated hydroxy groups into dithiocarbonates and their reduction with tributylstannane afforded, after removal of the protecting groups, (2R,4R)-1,1-bis(hydroxymethyl)-4-methoxycyclopentan-2-ol ((2R,4R)-17) and (3R,4R)-1,1-bis(hydroxymethyl)-4-methoxycyclopentan-3-ol (51). Reduction of a mixture of esters 35 and 36 gave (2R,3R)-2-benzyloxy-5-(hydroxymethyl)hexane-1,3,6-triol (52) as the major product and (2R,3S,4R)-3-benzyloxy-1,1-bis(hydroxymethyl)cyclopentane-2,4-diol (53) as the minor product. The latter was converted into (3R,4R)-1,1-bis(hydroxymethyl)cyclopentane-3,4-diol (58). 3-Deoxycarba analogues 51 and 58 arose by migration of benzoyl group in the preparation of the dithiocarbonates.

Pinching group stabilization. The synthesis and thermal isomerization of 10-Oxapentacyclo[6.3.2.13,6.01,8.02,7]tetradeca-4,12-diene

1984 ◽  
Vol 37 (6) ◽  
pp. 1293 ◽  
Author(s):  
DN Butler ◽  
RA Russell ◽  
RB Waring ◽  
RN Warrener
Keyword(s):  
Cyclic Ether ◽  
Major Product ◽  
The Novel ◽  
Lithium Aluminium Hydride ◽  
Group Effect ◽  
Flash Vacuum Pyrolysis ◽  
Lithium Aluminium ◽  
Vacuum Pyrolysis ◽  
Site Selective ◽  
Dimethyl Benzene

Sensitized irradiation (benzophenone, 0�, N2, pyrex filter, medium pressure Hg lamp) of dimethyl tricyclo[4.2.1.02,5]nona-3,7-diene-3,4-dicarboxylate (11) in (E)-1,2-dichloroethene yielded a mixture of 1 : 1 adducts (13) and (14) by site selective [2 π+2 π] cycloaddition at the cyclobutene π-bond. Reduction of the (Z)-dichloro isomer(13) with lithium aluminium hydride formed the related diol (16) which is the immediate precursor to the cyclic ether (18). Dechlorination of (18) with zinc in ethanol forms the title diene (19). Thermolysis of the polycyclic diester (20) affords the fragmentation products cyclopentadiene and dimethyl benzene-1,4-dicarboxylate. In contrast, the title compound (19) containing the cyclic ether ring was more stable and yielded the novel isomer (28) as the major product only upon flash vacuum pyrolysis at 560�(1.5 × 10-2 Torr). This difference in behaviour is attributed to a pinching group effect exerted by the cyclic ether present in (19).

Some oxidation products of lycoctonine revisited

2006 ◽  
Vol 84 (9) ◽  
pp. 1167-1173 ◽  
Author(s):  
Doaa Abdelrahman ◽  
Michael Benn ◽  
Ryan Hellyer ◽  
Masood Parvez ◽  
Oliver E Edwards
Keyword(s):  
Oxidation Product ◽  
Chromic Acid ◽  
Oxidation Products ◽  
Acid Oxidation ◽  
Lithium Aluminium Hydride ◽  
X Ray ◽  
X Ray Crystallography ◽  
Chromic Acid Oxidation ◽  
Lithium Aluminium ◽  
Norditerpenoid Alkaloid

The structure of a chromic acid oxidation product of the norditerpenoid alkaloid lycoctonine (1) was established as hydroxylycoctonal (3) by spectrometric analyses and X-ray crystallography of its reduction product, hydroxylycoctonine (5); the structure of lycoxonine, a chromic acid oxidation product of the lactam, lycoctonam (7), was similarly confirmed as N-ethyl-4,7,8-trihydroxy-1α,6β,14α,16β-tetramethoxy-19-oxoaconitane (8). Reduction of lycoxonine with lithium aluminium hydride gave the 1,14-di-O-methyl ether (12) of the bisnorditerpenoid alkaloid delbine (9).Key words: norditerpenoid, bisnorditerpenoid, alkaloids, lycoctonine, lycoctonam, hydroxylycoctonal, lycoxonine. 1,14-di-O-methyldelbine, semisynthesis.

Convenient Synthesis of (Z)-7- and (E)-9-dodecene-1-yl Acetate, Components of Some Lepidoptera Insect Sex Pheromone

2017 ◽  
Vol 68 (1) ◽  
pp. 180-185
Author(s):  
Adriana Maria Andreica ◽  
Lucia Gansca ◽  
Irina Ciotlaus ◽  
Ioan Oprean
Keyword(s):  
Sex Pheromone ◽  
Coupling Reaction ◽  
Coupling Scheme ◽  
Lithium Aluminium Hydride ◽  
Terminal Alkyne ◽  
Mercury Derivative ◽  
Lithium Aluminium ◽  
Convenient Synthesis ◽  
Practical Synthesis ◽  
Insect Sex

Were developed new and practical synthesis of (Z)-7-dodecene-1-yl acetate and (E)-9-dodecene-1-yl acetate. The routes involve, as the key step, the use of the mercury derivative of the terminal-alkyne w-functionalised as intermediate. The synthesis of (Z)-7-dodecene-1-yl acetate was based on a C6+C2=C8 and C8+C4=C12 coupling scheme, starting from 1,6-hexane-diol. The first coupling reaction took place between 1-tert-butoxy-6-bromo-hexane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-oct-7-yne, which is transformed in di[tert-butoxy-oct-7-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromobutane obtaining 1-tert-butoxy-dodec-7-yne. After acetylation and reduction with lithium aluminium hydride of 7-dodecyne-1-yl acetate gave (Z)-7-dodecene-1-yl acetate with 96 % purity. The synthesis of (E)-9-dodecene-1-yl acetate was based on a C8+C2=C10 and C10+C2=C12 coupling scheme, starting from 1,8-octane-diol. The first coupling reaction took place between 1-tert-butoxy-8-bromo-octane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-dec-9-yne, which is transformed in di[tert-butoxy-dec-9-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromoethane obtaining 1-tert-butoxy-dodec-9-yne. After reduction with lithium aluminium hydride of 1-tert-butoxy-(E)-9-dodecene and acetylation was obtained (E)-9-dodecene-1-yl acetate with 97 % purity.

3-(s-Hydrindacen-4-yl)propylamines and 4-(s-hydrindacen-4-yl)butylamines; Synthesis and pharmacological screening

1981 ◽  
Vol 46 (8) ◽  
pp. 1800-1807 ◽  
Author(s):  
Zdeněk Vejdělek ◽  
Marie Bartošová ◽  
Miroslav Protiva
Keyword(s):  
Malonic Acid ◽  
Local Anaesthetics ◽  
Lithium Aluminium Hydride ◽  
Spasmolytic Activity ◽  
Lithium Aluminium ◽  
Malonic Acid Derivatives ◽  
Pharmacological Screening ◽  
Hydroxyethyl Piperazine

4-Chloromethyl-s-hydrindacene (VIIa) was transformed via the malonic acid derivatives VIIIa and IXa to the acid Xb which afforded in four steps the homological acid Xc. Reactions of chlorides of both acids (XIbc ) with dimethylamine, 1-methylpiperazine and 1-(2-hydroxyethyl)piperazine led to the amides XIIbc-XIVbc which were reduced with lithium aluminium hydride to the title compounds IVcd-VIcd. The amines obtained show central neuroleptic effects only in subtoxic doses; they are also potent local anaesthetics and have significant spasmolytic activity of the neurotropic as well as musculotropic type.

Substituted N,N-Dimethyl-3-(phenylthio)- and -4-(phenylthio)benzylamines

1992 ◽  
Vol 57 (1) ◽  
pp. 194-203 ◽  
Author(s):  
Karel Šindelář ◽  
Vojtěch Kmoníček ◽  
Marta Hrubantová ◽  
Zdeněk Polívka
Keyword(s):  
Serotonin Receptors ◽  
Hydrobromic Acid ◽  
Antidepressant Activity ◽  
Benzoic Acids ◽  
Lithium Aluminium Hydride ◽  
Acid Chlorides ◽  
Activity Inhibition ◽  
Lithium Aluminium ◽  
The Brain

(Arylthio)benzoic acids IIa - IIe and VIb - VId were transformed via the acid chlorides to the N,N-dimethylamides which were reduced either with diborane "in situ" or with lithium aluminium hydride to N,N-dimethyl-(arylthio)benzylamines Ia - Ie and Vb - Vd. Leuckart reaction of the aldehydes IX and X with dimethylformamide and formic acid afforded directly the amines Va and Ve. Demethylation of the methoxy compounds Ia and Ve with hydrobromic acid resulted in the phenolic amines If and Vf. The most interesting N,N-dimethyl-4-(phenylthio)benzylamine (Va) hydrochloride showed affinity to cholinergic and 5-HT2 serotonin receptors in the rat brain and some properties considered indicative of antidepressant activity (inhibition of serotonin re-uptake in the brain and potentiation of yohimbine toxicity in mice).

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